DE102004027477A1 - 2-phenylethyl benzoate in oil-in-water cosmetic UV sunscreen emulsions - Google Patents

Abstract

cosmetic Water-in-oil emulsion, containing 2-phenylethyl benzoate.

Description

The The present invention relates to water-in-oil cosmetic emulsions containing 2-phenylethyl benzoate.

Of the Wish, nice and looking attractive, is inherently rooted in man. Even if the ideal of beauty has undergone changes over time, so is the pursuit of a flawless appearance always been the goal of the people. A substantial portion of one beautiful and attractive looks while the condition and appearance of the skin.

The Skin is the largest organ of the human. Among its many functions (for example, the heat control and as a sensory organ) is the barrier function, which is dehydration the skin (and ultimately the entire organism) prevents probably the most important. At the same time, the skin acts as a protection against the penetration and absorption of substances coming from outside. causes This barrier function is due to the epidermis, which as the outermost layer the actual protective cover across from of the environment. It is about one tenth of the total thickness at the same time the thinnest Layer of the skin.

In order to the skin can fulfill its biological functions to the full extent, it requires regular cleaning and care. The cleaning of the skin serves the removal of Dirt, sweat and leftovers Dead skin particles that provide an ideal breeding ground for pathogens and parasites of all kinds. Skin care products, usually creams, ointments or lotions, are mostly used for moisturizing and moisturizing of the skin. Often are added to them active ingredients that regenerate the skin and for example, their premature aging (e.g., the emergence of Pucker, To prevent and reduce wrinkles).

Skin Care Products usually consist of emulsions. Under emulsions understands one generally uses heterogeneous systems that do not consist of two or only limited to each other consist of miscible liquids, usually be referred to as phases and in which one of the two liquids in the form of the finest droplets in the other liquid is dispersed. externally and with mere When viewed in the eye, emulsions appear homogeneous.

are the two liquids Water and oil and oil droplets are fine dispersed in water, it is an oil-in-water emulsion (O / W emulsion, eg milk). The basic character of an O / W emulsion is characterized by the water. For a water-in-oil emulsion (W / O emulsion, z. As butter) is the reverse principle, the Basic character here by the oil is determined.

Around Emulsions over a longer one To keep the period stable and to prevent segregation of the phases Emulsifiers are added to the emulsions. For emulsifiers they are usually molecules with a polar, hydrophilic Structural element and a nonpolar, lipophilic structural element. In the late forties, a system was developed that made the selection of emulsifiers should facilitate. Each emulsifier becomes a so-called HLB value (a dimensionless number between 0 and 20, which after increments or tables (for example Fiedler, Lexikon der Hilfstoffe, Editio Cantor Verlag, Aulendorf) can be taken), indicating whether a preferred water or oil solubility is present. numbers under 9 indicate oil-soluble, hydrophobic emulsifiers, numbers above 11 water-soluble, hydrophilic.

at by far the most used in cosmetics emulsions these are O / W emulsions, because these are due to their watery Character easily into the skin without a long-lasting, sensory unattractive, greasy, sticky film on the skin.

Water-in-oil emulsions (W / O emulsions), however, have the advantage over O / W emulsions, that they are not traditional Preservatives must be protected from microbial decomposition, since the water phase as the locus of microorganisms through the outer oil phase microbial infestation is effectively protected.

Also W / O emulsions have the advantage compared to O / W emulsions to be relatively waterproof and in contact with water, for example when bathing, not so easy to be washed off the skin.

In particular, UV light protection preparations are, however, in exceptional cases based on W / O emulsions formulated. This is mainly due to the sensory properties (greasy, sticky) of this formulation. In particular, when higher light protection values are to be achieved, the preparations must contain high concentrations of oils which act as particularly greasy so that the UV light protection filters (in particular triazine derivatives) dissolve in sufficiently large amounts in the preparation.

It Therefore, the object of the present invention was cosmetic W / O emulsions (in particular cosmetic sunscreen preparations based on W / O emulsion) to develop, which have a much more pleasant sensors as preparations of the prior art. In particular, should The preparations do not feel sticky and quickly into the skin move in. Furthermore, it was the object of the present invention To develop formulations based on W / O emulsions, the a particularly high content of UV filter substances (in particular on triazine derivatives) and thus have a high and long-lasting Allow UV light protection. Not least, it was the object of the present invention, particularly waterproof develop cosmetic preparations.

• • eine kosmetische Wasser-in-Öl-Emulsion enthaltend 2-Phenylethylbenzoat, sowie durch
• • eine kosmetische Wasser-in-Öl-Emulsion enthaltend 2-Phenylethylbenzoat und ein oder mehrere UV-Filtersubstanzen aus der Gruppe der Triazinderivate.

The tasks are solved by surprise

• A cosmetic water-in-oil emulsion containing 2-phenylethyl benzoate, and by
• A cosmetic water-in-oil emulsion containing 2-phenylethyl benzoate and one or more UV filter substances from the group of triazine derivatives.

The inventive preparation has about that beyond more surprising Advantages over the preparations of the prior art. In particular, the leads Use of the 2-phenylethyl benzoate according to the invention to a particularly pleasant velvety-silky skin feeling, so that omitted in the preparations on the use of cyclomethicones can be. According to the invention advantageous are therefore cyclomethicone-free cosmetic preparations.

The inventive preparation is advantageous according to the invention characterized in that it contains 2-phenylethyl benzoate in a concentration from 0.5 to 20% by weight and according to the invention preferably from 2 to 10% by weight, each based on the total weight of the preparation contains.

und ist beispielsweise unter dem Handelsnamen X-Tend^TM 226 bei der Firma ISP erhältlich.The 2-phenylethyl benzoate (INCI: 2-phenylethyl benzoate) according to the invention has the following structure

and is available, for example, under the trade name X-Tend ^™ 226 from ISP.

When advantageous according to the invention W / O emulsifiers can surfactants Compounds are used which have an HLB value of 3 to 8.

According to the invention, preference is given to using one or more W / O emulsifiers selected from the group of the following compounds:
Sorbitan stearate, sorbitan oleate, lecithin, glyceryl lanolate, lanolin, ozokerite, hydrogenated castor oil, glyceryl isostearate, polyglyceryl-3-oleate, wool wax acid mixtures, wool wax alcohol mixtures, pentaerythritol isostearate, polyglyceryl-3-diisostearate, methyl glucose dioleate, PEG-7 hydrogenated castor oil, polyglyceryl-4-isostearate, Hexyl laurate, acrylate / C _10-30 alkyl acrylate crosspolymer, sorbitan isostearate, poloxamer 101, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-4-dipolyhydroxystearate, PEG-30 dipolyhydroxystearate, diisostearoylpolyglyceryl-3-diisostearate, polyglyceryl-3-dipolyhydroxystearate, polyglyceryl 3 dioleate.

Among others, the following combinations of lipophilic constituents and emulsifiers are advantageous according to the invention:
Sorbitan oleate mixed with hydrogenated castor oil, beeswax (Cera alba) and stearic acid, Natriumdihydroxycetylphosphat in admixture with isopropyl hydroxycetyl ether, methyl glucose dioleate mixed with hydroxystearate and beeswax, mineral oil in admixture with petrolatum, ozokerite, glyceryl oleate and lanolin alcohol, petrolatum in admixture with ozokerite, hydrogenated castor oil , Glyceryl isostearate and polyglyceryl-3-oleate, Sorbitan oleate mixed with PEG-2-hydrogenated castor oil, ozokerite and hydrogenated castor oil, sorbitan isostearate mixed with PEG-2-hydrogenated castor oil.

It is particular to the invention preferred if as W / O emulsifiers polyglyceryl-2 dipolyhydroxystearate or PEG-30 dipolyhydroxystearate.

advantageous embodiments of the present invention are characterized in that they are W / O emulsifiers in a total concentration of 0.1 to 10% by weight on the total weight of the preparation. According to the invention preferred it is there if the total concentration of W / O emulsifiers of 0.5 to 5% by weight, based on the total weight of the preparation is.

• • 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Aniso Triazin, erhältlich unter dem Handelsnamen Tinosorb S),
• • Dioctylbutylamidotriazon (INCI: Dioctylbutamidotriazone),
• • 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazin mit der (CAS Nr. 288254-16-0, erhältlich bei 3V Sigma unter der Handelsbezeichnung Uvasorb^® K2A),
• • 4,4',4''-(1,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoesäure-tris(2-ethylhexylester) (auch: 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazin (INCI: Octyl Triazone), welches von der BASF Aktiengesellschaft unter der Warenbezeichnung UVINUL^® T 150 vertrieben wird),

enthält.According to the invention, the preparation according to the invention is advantageously characterized in that the preparation contains one or more UV filter substances from the group of triazine derivatives selected from the group of compounds

• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: aniso triazine, available at the trade name Tinosorb S),
• Dioctylbutylamidotriazone (INCI: dioctylbutamidotriazone),
• • 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine with the (CAS Nr. 288254-16-0, available from 3V Sigma under the trade name Uvasorb K2A ^®),
• • 4,4 ', 4''- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) (also: 2,4,6-tris [ anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl Triazone), which is sold by BASF Aktiengesellschaft under the trade name Uvinul ^® T 150),

contains.

wobei R¹, R² und R³ unabhängig voneinander gewählt werden aus der Gruppe der verzweigten und unverzweigten Alkylgruppen mit 1 bis 10 Kohlenstoffatomen bzw. ein einzelnes Wasserstoffatom darstellen. Erfindungsgemäß besonders bevorzugt ist das 2,4-Bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Bis-Ethylhexyloxylphenol Methoxyphenyl Triazin), welches unter der Handelsbezeichnung Tinosorb^® S bei der CIBA-Chemikalien GmbH erhältlich ist. Ein weiteres bevorzugtes Bis-Resorcinyltriazinderivat ist das 2-[4,6-Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol (GAS Nr.: 2725-22-6).The triazine derivatives which are advantageous according to the invention also include bis-resorcinyl triazine derivatives. They are characterized by the following structural formula:

wherein R ¹ , R ² and R ^{3 are} independently selected from the group of branched and unbranched alkyl groups having 1 to 10 carbon atoms or represent a single hydrogen atom. Particularly preferred according to the invention is 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: Bis , which is available under the trade name Tinosorb ^® S from CIBA-Chemikalien GmbH -Ethylhexyloxylphenol methoxyphenyl triazine). Another preferred bis-resorcinyl triazine derivative is 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol (GAS No .: 2725- 22-6).

The Total amount of one or more bis-resorcinyl triazine derivatives in the finished cosmetic preparations is advantageous the range 0.01 wt .-% to 20 wt .-%, preferably from 0.1 to 10 % By weight selected, in each case based on the total weight of the preparations.

Particularly according to the invention preferred is the use of 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine as UV filter substance from the group of triazine derivatives.

Embodiments of the present invention which are advantageous according to the invention are characterized in that they contain UV filter substances from the group of triazine derivatives in a concentration of from 0.01 to 20% by weight based on the total weight of the preparation. In this case, a content of UV filter substances from the group of triazine derivatives in a concentration of 0.5 to 10% by weight, based on the total weight of the preparation, according to the invention is preferred.

It is advantageous according to the invention if the preparation according to the present Invention, further UV filter substances.

advantageous further UV filter substances in the context of the present invention are those mentioned below, which are in the water and / or the oil phase may be present.

Advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: octocrylene) and esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate (2-ethylhexyl) Ethylhexyl 4-methoxycinnamate, INCI: octyl methoxycinnamate) and isopentyl 4-methoxycinnamate (isopentyl 4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate), 3- (4- (2,2-bis ethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / Dimethylsiloxane copolymer, which is available, for example, under the trade name Parsol ^® SLX from Hoffmann La Roche.

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS-Nr. 70356-09-1), marketed by Givaudan under the trade name Parsol ^® 1789 and is sold by Merck under the trade name Eusolex ^® 9020th

worin
R¹ und R² unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₃-C₁₀-Cycloalkyl oder C₃-C₁₀-Cycloalkenyl bedeuten, wobei die Substituenten R¹ und R² gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-Ring bilden können und R³ einen C₁-C₂₀-Alkyl Rest bedeutet.Further advantageous UV-A filter substances in the context of the present invention are hydroxybenzophenones, which are distinguished by the following structural formula:

wherein
R ¹ and R ² independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl or C ₃ -C ₁₀ -cycloalkenyl, where the substituents R ¹ and R ² together with the nitrogen atom to which they are attached are bonded, can form a 5- or 6-membered ring and R ^{3 is} a C ₁ -C ₂₀ -alkyl radical.

und unter dem Uvinul A Plus bei der Fa. BASF erhältlich ist.A particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2'-hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone), which has the following structure:

and Uvinul A Plus is available from BASF.

• • Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolammonium-Salze, insbesondere das Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz mit der INCI-Bezeichnung Bisimidazylate (CAS-Nr.: 180898-37-7), welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist;
• • Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phenylbenzimidazole Sulfonsäure (CAS.-Nr. 27503-81-7), welches beispielsweise unter der Handelsbezeichnung Eusolex 232 bei Merck oder unter Neo Heliopan Hydro bei Haarmann & Reimer erhältlich ist;
• • 1,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol (auch: 3,3'-(1,4-Phenylendimethylene)-bis-(7,7-dimethyl-2-oxo-bicyclo-[2.2.1 ]hept-1-ylmethan Sulfonsäure) und dessen Salze (besonders die entprechenden 10-Sulfato-verbindungen, insbesondere das entsprechende Natrium-, Kalium- oder Triethanolammonium-Salz), das auch als Benzol-1,4-di(2-oxo-3-bornylidenmethyl-10-sulfonsäure) bezeichnet wird. Benzol-1,4-di(2-oxo-3-bornyli denmethyl-10-sulfonsäure) hat die INCI-Bezeichnung Terephtalidene Dicampher Sulfonsäure (CAS.-Nr.: 90457-82-2) und ist beispielsweise unter dem Handelsnamen Mexoryl SX von der Fa. Chimex erhältlich;
• • Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bornylidenmethyl)-benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und deren Salze.

Advantageous further UV filter substances in the context of the present invention are sulfonated, water-soluble UV filters, such as. B .:

• Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene-1,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammoni salt and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which is available, for example, under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer;
• 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo) bicyclo [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt), also known as benzene-1,4 benzene-1,4-di (2-oxo-3-bornylmethylenedi-10-sulphonic acid) has the INCI name Terephtalidene Dicampher sulphonic acid (CAS. No. 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex;
• Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof.

advantageous UV filter substances in the context of the present invention are further so-called broadband filters, i. Filter substances containing both UV-A as well as absorb UV-B radiation.

An advantageous broadband filter for the purposes of the present invention is also the 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which is available under the trade name Tinosorb ^® M from CIBA-Chemikalien GmbH.

Favorable Broadband filter according to the present invention is also the 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.

• • 3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3-Benzylidencampher;
• • 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2-ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;
• • Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhexyl)-ester;
• • Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone), welches unter der Handelsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist;
• • Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Methoxyzimtsäureisopentylester;
• • Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon sowie
• • an Polymere gebundene UV-Filter.

The other UV filter substances can be oil-soluble or water-soluble. Advantageous oil-soluble filter substances are z. B .:

• 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester;
• Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;
• Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone), which is available under the trade name UVASORB HEB from Sigma 3V;
• Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and
• • polymer-bound UV filters.

These additional UV filter substances can According to the invention advantageous in a total concentration of 0.01 to 20% by weight and preferred according to the invention in a total concentration of 0.5 to 10% by weight, respectively based on the total weight he preparation contained in this be.

Furthermore, the preparation according to the invention can advantageously contain UV sunscreen filter substances based on inorganic pigments. Preferred inorganic pigments are metal oxides and / or other water-insoluble or insoluble metal compounds, in particular oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon ( SiO ₂ ), manganese (for example MnO), aluminum (Al ₂ O ₃ ), cerium (for example Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides and also the barium sulfate (BaSO ₄ ).

The Pigments can advantageous in the context of the present invention also in the form of a commercial available oily or aqueous predispersions come into use. These predispersions may advantageously dispersants and / or solubilization promoters may be added.

The Pigments can According to the invention advantageous superficial be treated ("coated"), for example a hydrophilic, amphiphilic or hydrophobic character formed should be or should be preserved. This surface treatment can consist of that the pigments according to known methods with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer be provided. The different surface coatings can be used in the According to the present invention also contain water.

Inorganic surface coatings for the purposes of the present invention may consist of aluminum oxide (Al ₂ O ₃ ), aluminum hydroxide Al (OH) ₃ or aluminum oxide hydrate (also: Alumina, CAS No .: 1333-84-2), sodium hexametaphosphate (NaPO ₃ ) ₆ , sodium metaphosphate (NaPO ₃ ) _n , silicon dioxide (SiO ₂ ) (also: silica, CAS No .: 7631-86-9), barium sulfate (BaSO ₄ ) or iron oxide (Fe ₂ O ₃ ). These inorganic surface coatings may be present alone, in combination and / or in combination with organic coating materials.

organic surface coatings For the purposes of the present invention may consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length from 200 to 350 dimethylsiloxane units and silica gel) or alginic acid. These organic surface coatings can alone, in combination and / or in combination with inorganic Coating materials occur.

Zinc oxide particles which are suitable according to the invention and predispersions of zinc oxide particles are obtainable from the following companies under the following commercial names:

Suitable titanium dioxide particles and predispersions of titanium dioxide particles are available from the following companies under the following trade names:

The Water phase of the W / O emulsion of the preparation according to the invention may advantageously conventional cosmetic Excipients such as alcohols, in particular Such low C number, preferably ethanol and / or isopropanol, Diols or polyols of low C number and their ethers, preferably Propylene glycol, glycerol, butylene glycol, ethylene glycol, ethylene glycol monoethyl or -monobutyl ether, propylene glycol monomethyl, -monoethyl- or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, polymers, foam stabilizers, electrolytes and in particular one or more thickening agents, which or which are chosen favorably can be from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for. Hyaluronic acid, xanthan gum, hydroxypropyl methylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of the so-called Carbopole [from the Bf. Goodrich], for example Carbopols of the types 980, 981, 1382, 2984, 5984, ETD 2020, ETD 2050, Ultrez 10, one at a time or in combination.

The preparations according to the invention can furthermore advantageously also contain self-tanning substances, such as dihydroxyactone and / or melanin derivatives in concentrations from 1% by weight up to 10% by weight, based on the total weight of the Preparation.

Furthermore, the preparations according to the invention can also be advantageous for repellents for protection Mosquitoes, ticks and spiders and the like included. Advantageous z. N, N-diethyl-3-methylbenzamide (trade name: meta-delphphene, "DEET"), dimethyl phthalate (trade name: palatinol M, DMP), 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, and especially 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (available under the trade name insect repellent ^® 3535 from Fa. Merck). the repellents may be used as well in combination, both separately.

When Humectants (moisturizers) become substances or mixtures of substances denotes which cosmetic preparations impart the property, after application or spreading on the skin surface, the moisture release the horny layer (also called transepidermal water loss (TEWL)) to reduce and / or the hydration of the horny layer positive influence.

Advantageous humectants (moisturizers) for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccharide gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gellable polysaccharides. Hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, for example, which are filed in the Chemical Abstracts under the registry number 178463-23-5 and z. B. under the name Fucogel ^® 1000 of the company SOLABIA SA is available. Moisturizers can also be used advantageously as anti-wrinkle active ingredients for protection against skin changes, as described, for example, in US Pat. B. occur during skin aging, can be used.

It is advantageous in the context of the present invention, when the preparation according to the invention one or more humectants in a total concentration from 0.1 to 20% by weight and preferably in a total concentration from 0.5 to 10% by weight, based in each case on the total weight the preparation contains.

The cosmetic preparations according to the invention may also advantageously, although not necessarily, contain fillers which are e.g. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or enhance a velvety or silky feel on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as, for example, tapioca starch, distarch phosphate, aluminum or sodium starch, octenylsuccinate and the like), pigments which have neither chiefly UV filter nor coloring action (such as, for example, US Pat. B. boron nitride etc.) and / or Aerosils ^® (CAS no. 7631-86-9).

The oil phase of W / O emulsion of the preparation according to the invention is chosen favorably from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12 to 18 carbon atoms. The fatty acid triglycerides for example chosen favorably are selected from the group of synthetic, semisynthetic and natural oils, such as z. B. cocoglyceride, olive oil, Sunflower oil, Soybean oil, Peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grapeseed oil, safflower oil, evening primrose oil, macadamia nut oil and the like.

According to the invention advantageous are also z. Natural Waxes of animal and vegetable origin, such as Beeswax and other insect waxes as well as berry wax, shea butter and / or Lanolin (wool wax).

Further advantageous polar oil components can for the purposes of the present invention are further selected from the group of Esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms and from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then chosen advantageous are from the group octyl palmitate, octyl cocoate, octyl isostearate, Octyldodeceyl myristate, octyldodecanol, cetearyl isononanoate, isopropyl myristate, Isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyl dodecyl palmitate, Stearylheptanoate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, Tridecyl stearate, tridecyl trimellitate, as well as synthetic, semisynthetic and natural Mixtures of such esters, such as. B. jojoba oil.

Further can the oil phase chosen favorably are from the group of dialkyl ethers and dialkyl, advantageous are z. B. dicaprylyl ether (Cetiol OE and / or dicaprylyl carbonate, for example, under the trade name Cetiol CC at the Cognis available.

It is further preferred that the oil component from the group consisting of isoeicosane, neopentyl glycol, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol dicaprylate / dicaprate, C ₁₂ - ₁₃ alkyl lactate, di-C _12-13 -Alkyltartrat, triisostearin, Dipentaerythrityl Hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricaprylin, dimethylisosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C _12-15 alkyl benzoate or consists entirely of this.

Advantageous oil components are also z. B. Butyloctylsalicylate (for example, the under the trade name Hallbrite BHB available from the company CP Hall), Hexadecyl benzoate and butyl octyl benzoate and mixtures thereof (Hallstar AB) and / or diethylhexylnaphthalate (Hallbrite TQ or Corapan TQ from H & R).

Also any mixtures of such oil and wax components are advantageous in the sense of the present Use invention.

Further can the oil phase also advantageously contain nonpolar oils, for example those who chose are from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, Vaseline (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and isohexadecane. Among the polyolefins, polydecenes are the preferred substances.

Advantageous can the oil phase also have a content of cyclic or linear silicone oils or Completely from such oils although it is preferred, except the silicone oil or silicone oils additional Content of other oil phase components to use.

werden auch als Polydimethylsiloxan bzw. Dimethicon (INCI) bezeichnet. Dimethicone gibt es in verschiedenen Kettenlängen bzw. mit verschiedenen Molekulargewichten.Silicone oils are high molecular weight synthetic polymeric compounds in which silicon atoms via oxygen atoms chain and / or net-like linked and the remaining valences of silicon by hydrocarbon radicals (usually methyl, more rarely ethyl, propyl, phenyl groups, etc.) are saturated. Systematically, the silicone oils are called polyorganosiloxanes. The methyl-substituted polyorganosiloxanes, which are the quantitatively most important compounds of this group and are characterized by the following structural formula

are also referred to as polydimethylsiloxane or dimethicone (INCI). Dimethicones are available in different chain lengths or with different molecular weights.

Especially advantageous polyorganosiloxanes in the context of the present invention are, for example, dimethylpolysiloxanes [poly (dimethylsiloxane)], which, for example, under the trade names Abil 10 bis 10,000 available from Th. Goldschmidt are. Also advantageous are phenylmethylpolysiloxanes (INCI: phenyl dimethicone, Phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI also called cyclomethicones amino-modified silicones (INCI: amodimethicone) and silicone waxes, e.g. B. Polysiloxane-polyalkylene copolymers (INCI: Stearyl dimethicones and cetyl dimethicones) and dialkoxydimethylpolysiloxanes (Stearoxy dimethicone and behenoxy stearyl dimethicone) which as different Abil wax types are available from Th. Goldschmidt. But also other silicone oils are advantageous for the purposes of the present invention to use for example, cetyl dimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, Poly (methylphenylsiloxane).

• (a) Siloxanelastomere, welche die Einheiten R₂SiO und RSiO_1,5 und/oder R₃SiO_0,5 und/oder SiO₂ enthalten, wobei die einzelnen Reste R jeweils unabhängig voneinander Wasserstoff, C_1-24-Alkyl (wie beispielsweise Methyl, Ethyl, Propyl) oder Aryl (wie beispielsweise Phenyl oder Tolyl), Alkenyl (wie beispielsweise Vinyl) bedeuten und das Gewichtsverhältnis der Einheiten R₂SiO zu RSiO_1,5 aus dem Bereich von 1 : 1 bis 30 : 1 gewählt wird;
• (b) Siloxanelastomere, welche in Silikonöl unlöslich und quellfähig sind, die durch die Additionsreaktion eines Organopolysiloxans (1), das siliciumbebundenen Wasserstoff enthält, mit einem Organopolysiloxan (2), das ungesättigte aliphatische Gruppen enthält, erhältlich sind, wobei die verwendeten Mengenateile so gewählt werden, dass die Menge des Wasserstoffes des Organopolysiloxans (1) oder der ungesättigten aliphatischen Gruppen des Organopolysiloxans (2) • im Bereich von 1 bis 20 mol-% liegt, wenn das Organopolysiloxan nicht zyklisch ist und • im Bereich von 1 bis 50 mol-% liegt, wenn das Organopolysiloxan zyklisch ist.

The preparations according to the invention may furthermore advantageously comprise one or more substances from the following group of siloxane elastomers, for example in order to increase the water resistance and / or the sun protection factor of the products:

• (A) siloxane elastomers containing the units R ₂ SiO and RSiO _1.5 and / or R ₃ SiO _0.5 and / or SiO ₂ , wherein the individual radicals R are each independently hydrogen, C _1-24 alkyl (as for example, methyl, ethyl, propyl) or aryl (such as phenyl or tolyl), alkenyl (such as vinyl) and the weight ratio of the units R ₂ SiO to RSiO _1.5 from the range of 1: 1 to 30: 1 is elected;
• (b) Siloxane elastomers which are insoluble and swellable in silicone oil obtainable by the addition reaction of an organopolysiloxane (1) containing silicon-bonded hydrogen with an organopolysiloxane (2) containing unsaturated aliphatic groups, the proportions used being such in that the amount of hydrogen of the organopolysiloxane (1) or of the unsaturated aliphatic groups of the organopolysiloxane (2) is in the range from 1 to 20 mol%, if the organopolysiloxane is not cyclic and is in the range from 1 to 50 mol% % is when the organopolysiloxane is cyclic.

Advantageous For the purposes of the present invention, the siloxane elastomer (s) are present in the form of spherical Powder or in the form of gels.

According to the invention advantageous in the form of spherical Powder present siloxane elastomers are those with the INCI name Dimethicone / Vinyl Dimethicone Crosspolymer, for example that of DOW CORNING under the trade designations DOW CORNING 9506 Powder available.

Especially it is preferred if the siloxane elastomer in combination with oils Hydrocarbons of animal and / or vegetable origin, synthetic oils, synthetic Esters, synthetic ethers or mixtures thereof is used.

All it is particularly preferred if the siloxane elastomer in combination with unbranched at room temperature liquid or pasty silicone oils or cyclic silicone oils or mixtures thereof is used. Particularly advantageous Organopolysiloxane elastomers with the INCI name Dimethicone / Polysilicone-11, especially those available from Grant Industries Inc. Gransil types GCM, GCM-5, DMG-6, CSE gel, PM gel, LTX, ININ gel, AM-18 gel and / or DMCM-5.

All exceptionally preferred it is when the siloxane elastomer is in the form of a gel of siloxane elastomer and a lipid phase, wherein the content of the siloxane elastomer in which gel is 1 to 80% by weight, preferably 0.1 to 60% by weight, respectively based on the total weight of the gel.

It is advantageous in the context of the present invention, the total amount the siloxane elastomers (active content) from the range of 0.01 to 10 wt .-%, advantageously from 0.1 to 5 wt .-%, each based on the total weight of the formulation to choose.

Especially advantageous preparations are also obtained if, as additional or agents used antioxidants. Included in the invention the preparations advantageously one or more antioxidants. As cheap, but yet optional antioxidants can all be used for cosmetic Applications suitable or common Antioxidants are used.

Especially For the purposes of the present invention, water-soluble antioxidants may be advantageous be used, such as vitamins, eg. As ascorbic acid and their derivatives.

preferred Antioxidants are also vitamin E and its derivatives as well as vitamin A and its derivatives.

The Amount of antioxidants (one or more compounds) in the Preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20 Wt .-%, in particular 0.1 to 10 wt .-%, based on the total weight the preparation.

Provided Vitamin E and / or derivatives thereof are the antioxidant (s), is advantageous, their respective concentrations from the field from 0.001 to 10% by weight, based on the total weight of the formulation, to choose.

Provided Vitamin A or vitamin A derivatives, or carotenes or their derivatives the one or more antioxidants are advantageous, their respective Concentrations from the range of 0.001 to 10 wt .-%, based on the total weight of the formulation to choose.

It is particularly advantageous when the cosmetic preparations according to the present Contain cosmetic active ingredients, preferred agents Antioxidants are what protect the skin from oxidative stress protect can.

Further advantageous active ingredients in the context of the present invention are natural active ingredients and / or derivatives thereof, such as. Alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, creatinine, tauriine and / or β-alanine, and 8-hexadecene-1,16- dicarboxylic acid (dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid) and / or licochalcone A, which is characterized by the following structural formula:

licochalcone may also be used advantageously as a component of plant extracts, in particular of aqueous radix Glycyrrhizae inflatae, are used.

It is advantageous according to the invention when the cosmetic preparations 0.001 to 10 wt .-%, in particular 0.05 to 5 wt .-%, especially 0.01 to 2 wt .-% of an extract from Radix Glycyrrhizae inflatae, in each case based on the Total weight of the preparation.

All it is particularly advantageous to start from an extract which under the name Polyol Soluble Licorice Extract PU (INCI name Glycyrrhiza Inflata) can be obtained from the company Maruzen. The extract from Radix Glycyrrhizae inflatae contains about 25% % Licochalcone A.

Inventive formulations, which z. B. known anti-wrinkling agents such as flavone glycosides (especially α-glycosyl rutin), Coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for protection against aesthetics unattractive skin changes, as they are z. B. occur during skin aging (such as Dryness, roughness and formation of dry wrinkles, itching, reduced refatting (eg after washing), visible vascular dilations (telangiectasias, Cuperosis), slackness and development of wrinkles and wrinkles, local hyper-, hypo- and false pigmentations (eg age spots), increased susceptibility across from mechanical stress (eg cracking) and the like). Farther Advantageously, they are suitable against the appearance of dry or rough skin.

The cosmetic preparations according to the invention can contain cosmetic excipients, such as those commonly used in such preparations be used, for. Preservatives, preservatives, Complexing agents, bactericides, perfumes, preventing substances or increasing the foaming, dyes, Pigments that have a coloring Have effect, thickener, moisturizing and / or moisturizing Substances, fillers, the skin feeling improve, fats, oils, Waxes or other usual Components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

According to the invention preferred are preparations that are free of preservatives.

Advantageous For the purposes of the present invention are preparations for care the skin: they can do that cosmetic sunscreen, also as a make-up product in the decorative Cosmetics serve. A further advantageous embodiment of the present invention Invention consists in after-sun products.

Corresponding their structure can cosmetic compositions according to the present invention, For example, be used as skin protection cream, day cream or night cream, etc. It may be possible and advantageously, the compositions of the invention as a basis for pharmaceutical To use formulations.

It is also advantageous in the context of the present invention to prepare cosmetic preparations, the main purpose of which is not to protect against sunlight but which nevertheless contains a content of UV protective substances. So z. B. in day creams or makeup products usually incorporated UV-A or UV-B filter substances. Also UV protection substances, as well as antioxidants and, if desired, preservatives, an effective protection of the preparations themselves against spoilage. Also favorable are cosmetic preparations which are in the form of a sunscreen.

to Application are the cosmetic preparations according to the invention in the for Cosmetics usual Applied to the skin and / or hair in sufficient quantity.

The The following examples are intended to illustrate the present invention, without restricting it. All Quantities, percentages and percentages are, unless otherwise stated indicated on the weight and the total amount or on the total weight the preparations.

UVASorb^® K2A

= 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazin [CAS Nr. 288254-16-0]

Uvinul^® A Plus

= 2-(4'-Diethylamino-2'-hydoxybenzoyl)-benzoesäurehexylester (auch: Aminobenzophenon)

1. Dünnflüssige bis sprühbare W/O-Emulsionen

2. W/O Emulsionen (Cremes & Lotions)

In the following examples,

Uvasorb® ^® K2A

= 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine [CAS no. 288254-16-0]

Uvinul ^® A Plus

= 2- (4'-diethylamino-2'-hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone)

1. Thin-liquid to sprayable W / O emulsions

2. W / O emulsions (creams & lotions)

Claims (10)

Cosmetic water-in-oil emulsion containing 2-phenylethyl benzoate. Cosmetic water-in-oil emulsion containing 2-phenylethyl benzoate and one or more UV filter substances from the group of triazine derivatives. Preparation according to claim 2, characterized in that that the preparation of one or more UV filter substances the group of triazine derivatives selected from the group of the compounds 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5- triazine, Dioctylbutylamidotriazone, 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine, 4, 4 ', 4' '- (1,3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethylhexyl) contain. Preparation according to one of the preceding claims, characterized in that it contains 2-phenylethyl benzoate in a concentration from 2 to 10% by weight, based on the total weight of the preparation, contains. Preparation according to one of the preceding claims, characterized characterized in that they UV filter substances from the group of Triazine derivatives in a concentration of 0.1 to 10% by weight, based on the total weight of the preparation contains. Preparation according to one of the preceding claims, characterized in that as w / o emulsifier sorbitan stearate, sorbitan oleate, lecithin, glyceryl lanolate, lanolin, ozokerite, hydrogenated castor oil, glyceryl isostearate, polyglyceryl-3-oleate, wool wax acid mixtures, wool wax alcohol mixtures, pentaerythrityl isostearate, polyglyceryl-3 diisostearate, methyl glucose dioleate, PEG-7 hydrogenated castor oil, polyglyceryl-4 isostearate, hexyl laurate, acrylate / C _10-30 alkyl acrylate crosspolymer, sorbitan isostearate, poloxamer 101, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl dipolyhydroxystearate-4, PEG-30 dipolyhydroxystearate, diisostearoylpolyglyceryl-3-diisostearate, polyglyceryl-3-dipolyhydroxystearate and / or polyglyceryl-3-dioleate. Preparation according to one of the preceding claims, characterized characterized in that as W / O emulsifier polyglyceryl-2 dipolyhydroxystearate or PEG-30 dipolyhydroxystearate. Preparation according to one of the preceding claims, characterized characterized in that they are W / O emulsifiers in a total concentration from 0.5 to 10% by weight, based on the total weight of the preparation, contains. Preparation according to one of the preceding claims, characterized in that the preparation contains further UV filter substances contains. Preparation according to one of the preceding claims, characterized characterized in that they contain one or more humectants in one Total concentration of 0.5 to 10% by weight, based on the total weight the preparation contains.